The coordination properties and the photophysical response of a new cyclam fluorescent probe for Zn(II), [L1H: 1-(benzimidazol-2-ylmethyl]-1,4, 8,11-tetraazacyclotetradecane] toward Cu(II), Zn(II), and Cd(II) are reported. The stability constants of the corresponding complexes were determined by means of potentiometric measurements in aqueous solution. The fluorescence of L1H was quenched by the presence of Cu(II), and L1H behaves as an OFF ON sensor for Zn(II) even in the presence of a wide range of biological divalent cations. Furthermore, on addition of successive amounts of Zn(II), the fluorescence emission of L1H increases linearly by a factor of 12. This can be correlated to the efficient Zn(II) binding of L1H and to the participation of all the amine functions in the metal coordination which prevents the photoincluced electron transfer (PET) effect and promotes a good chelation-enhanced fluorescence (CHEF) effect; this confers to the cyclam probe better sensing properties than the cyclen ionophore.